Detergents and cleansers

ABSTRACT

NOVEL DETERGENT AND CLEANING AGENTS ARE DISCLOSED CHARACTERIZED BY THEIR ABILITY TO INHIBIT THE GRAYING OF TEXTILE ARTICLES WHICH TAKES PLACE IN LAUNDERING. IN PARTICULAR THE NOVEL DETERGENT AND CLEANSING AGENTS ARE EFFECTIVE TO PREVENT THE GRAYING OF TEXTILE ARTICLES PREPARED AT LEAST IN PART WITH SYNTHETIC FIBERS. THE DETERGENT AND CLEANSING AGENTS OF THE INVENTION ARE CHARACTERIZED BY A CONTENT OF 0.1 TO 20 WT, PERCENT REFERRED TO THE TOTAL COMPOSITION OF AT LEAST ONE WATER SOLUBLE SALT OF A FREE CARBOXYL GROUP CONTAINING POLYESTERS, THE ACID AND ALCOHOL RADICALS OF WHICH RESPECTIVELY ARE DERIVED FROM TRICARBOXYLIC AND/OR TETRACARBOXYLIC ACIDS AND BIVALENT ALCOHOLS. IN ADDITION TO THE AFORESAID POLYESTER SALTS THE DETERGENT AND CLEANING AGENTS CONTAIN THE CONVENTIONAL SURFACE ACTIVE MATERIALS AND THE USUAL ADDITIVES SUCH AS OPTICAL BRIGHTENERS, BLEACHING AGENTS, SUDSERS, ANTIFOAMERS, ETC.

XR 3563963 EX 3,563,903 DETERGENTS AND CLEANSERS Edmund Schmadel, Duaseldorf-Benrath, and Walter Kling, Dusseldorf-Ellen Germany, assignors to Henkel & Cie GmbH, Dusseldorf, Germany, a corporation of Germany No Drawing. Filed Nov. 17, 1967, Ser. No. 683,778 Claims priority, application Germany, Nov. 19, 1966, P 16 17 122.5 Int. Cl. Clld 3/26 US. Cl. 252-152 3 Claims ABSTRACT OF THE DISCLOSURE Novel detergent and cleansing agents are disclosed characterized by their ability to inhibit the graying of textile articles which takes place in laundering. In particular the novel detergent and cleansing agents are effective to prevent the graying of textile articles prepared at least in part with synthetic fibers.

The detergent and cleansing agents of the invention are characterized by a content of 0.1 to 20 wt. percent referred to the total composition of at least one water soluble salt of a free carboxyl group containing polyester, the acid and alcohol radicals of which respectively are derived from tricarboxylic and/or tetracarboxylic acids and bivalent alcohols. In addition to the aforesaid polyester salts the detergent and cleaning agents contain the conventional surface active materials and the usual additives such as optical brighteners, bleaching agents, sudsers, antifoamers, etc.

' This invention relates to detergent and cleaning agents characterized by their ability to inhibit the graying of textile articles in laundering.

More particularly this invention relates to detergent and cleaning agents containing water-soluble salts of freecarboxyl group containing polyesters.

It is known in the prior art to add to detergents and cleansers containing surface active compounds, substances which improve the dirt carrying and retaining ability of the washing solutions. Such substances, which are referred to hereinafter as graying inhibitors, prevent a resorption of the dissolved dirt onto the cleaned surfaces. These substances are usually polyanionic polymers which are manufactured from natural substances such as cellulose, gelatins or glue, or are prepared by the polymerization of vinyl compounds, such as acrylic acid, methacrylic acid, maleic acid and mixtures thereof with copolymerizable olefins. Further, the polysulfonates of vinyl polymers have already been proposed as useful gray-inhibiting additives for detergent and cleanser preparations. Of all of the proposed compounds, however, only carboxymethylcellulose has achieved any great technical importance, inasmuch as its gray-inhibiting action excels that of any synthetic polymers that have become known. However, carboxymethylcellulose as well as the above-named synthetic polymers have the disadvantage that their gray-inhibiting action is limited to cellulose fibers, whereas they are practically ineffectual in the washing of synthetic fiber material, particularly materials prepared from polyamides, polyesters and polyolefins. This disadvantage is particularly noticeable in connection with white textiles made of synthetic fibers'or mixed fabrics made of synthetic and cellulose fibers, i.e., polyester-cotton mixtures, which turn irreversibly gray in use despite repeated washing and thus become unattractive and must be discarded.

It is therefore a primary object of this invention to provide new and improved detergent compositions having increased gray-inhibiting efficiency over previously known detergent compositions.

3,563,903 Patented Feb. 16, 1971 Another object is to provide improved detergent compositions containing as the gray-inhibiting agent, a watersoluble salt of a free carboxyl group containing polyester.

A yet further object is to provide improved gray-inhibiting detergent compositions which are surprisingly effective in laundering textile articles prepared at least in part with synthetic fibers.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter.

It has now surprisingly been found that water-soluble salts of free carboxyl group containing polyesters, the acid radicals of which are derived from a tricarboxylic and/or tetracarboxylic acid and whose alcohol radicals are derived from bivalent alcohols possess gray-inhibiting properties to an exceptional degree.

As mentioned above, it has already been proposed to combine synthetic detergent compounds with various graying inhibitors to produce anti-graying detergent compositions. As far as is known, however, no one prior to this invention has discovered the particular combination of compounds and proportions described herein that offer extraordinary results in the important area of whiteness maintenance and whiteness retention.

These and other advantages are obtained according to this invention by providing detergent compositions comprising a detergent surfactant compound and as a graying inhibitor 0.1 to 20 wt. percent referred to the total detergent compositions of a free carboxyl group containing polyester, the acid radicals of which are derived from tricarboxylic and/or tetracarboxylic acids'and the alcohol radicals of which are derived from compounds having two aliphatic hydroxyl groups.

Polyesters can also be used to produce the same effect in which up to 50 mole percent of the trior tetracarboxylic acid radicals have been replaced by dicarboxylic acid radicals.

The polyester salts as used in the detergent compositions of the invention are manufactured by prior-art methods.

The starting materials are aliphatic, cycloaliphatic and aromatic tricarboxylic and tetracarboxylic acids and mixtures thereof. Instances of especially suitable acids are citric acid, tricarballylic acid, nitrilotriacetic acid, ethylenediaminotetracetic acid, cyclohexanetricarboxylic acid, trimesic acid, oxytrimesic acid and pyromellitic acid. The aforesaid acids may be replaced in amounts of up to 50 mole percent, by saturated or unsaturated aliphatic, cycloaliphatic or aromatic dicarboxylic acids, such as for example, malonic, succinic, glutaric, adipic, sebacic, maleic and fumaric acid, as well as by benzenedicarboxylic acids. The polyvalent carboxylic acids used generally contain 6 (citric-see examples) up to 20 carbon atoms.

The compounds having two aliphatic hydroxyl groups, i.e., the compounds from which the alcohol component is derived, may contain aliphatic, cycloaliphatic, araliphatic, straight-chain or branched, saturated or unsaturated hydrocarbon radicals as well as hetero atoms such as O, N and S. Instances of suitable hydroxyl compounds are aliphatic diols having 2 to 18, preferably 2 to 8 carbon atoms such as for example ethylene glycol, propanediol-1,3, propanediol-l,2, butanediol-1,3, hexanediol-l,6, heptanediol-l,7, and 2,2-diethylpropanediol-l,3; ether alcohols such as dior tripropylene glycol, glycerine monoalkyl ether and thiodiethylene glycol. Illustrative of the starting substances having cyclic hydrocarbon radicals are the following: cyclohexanediol and those bivalent phenols,

, the hydroxyl groups of which are etherified with aliphatic radicals contain 1 to 6, preferably 1 to 3, carbon atoms, and the alkyl, aryl or alkylaryl radicals contain up to 18 carbon atoms. Such compounds include, for example, N-methyldiethanolamine, N-methyldipropanolamine, N- ethyldiethanolamine, N-butyldiethanolamine, N-dodecyldiethanolamine, N-cyclohexyldipropanolamine and N- phenyldiethanolamine.

The preparation of the polyesters is carried out by the conventional methods, as for example, by heating the mixture of starting materials for several hours under normal pressure or in vacuo, in the presence in either case of a solvent with which the water of reaction can be removed azeotropically by distillation. The reaction can be accelerated by the addition of common esterification catalysts, especially strong inorganic or organic acids. Instead of the free di-, trior tetracarboxylic acids, the anhydrides and halides of these acids can also be used as starting materials. Particularly suitable in this connection are the dihalides. Similarly, the polyvalent carboxylic acids, in the form of their diesters derived from univalent alcohols of low molecular weight, can be re-esterified with the bivalent alcohols in the presence of known reesterification catalysts, in the conventional manner. Examples of such diesters are citric acid dimethyl ester and pyromellitic acid diethyl ester. If alkaline re-esterification catalysts are used, care must be taken to see that they are still present in sufiicient excess after the neutralization of the free carboxyl groups.

By selecting the molar ratio of polycarboxylic acid to bivalent alcohol within a preferred range of l.l::9 to 0.9: 1.1, it is possible to vary the degree of polymerization within certain limits. In the interest of a good anti-graying action, a high degree of polymerization is desirable. To prevent a premature interruption of chain formation, therefore, a molar ratio is preferred that is as close as possible to 1:1.

The polyesters containing free carboxyl groups and manufactured in the above-described manner are of a resin-like nature, substantially insoluble inwater and in organic solvents, but easily soluble in dilute alkali lyes. They may also contain secondary amounts of esters of low molecular weight and of unreacted starting substances which can be removed by extraction with organic solvents and thereafter recycled for further reaction. As these compounds, however, do not impair the cleaning properties of the agents, such separation is generally unnecessary.

As a result of the insolubility of the high molecular compounds in organic solvents, and because of their content of low-molecular constituents, the usual methods utilized for molecular weight determination are inoperative. Therefore, it is not possible to state the degree of polymerization and molecular weight of the polyesters with complete accuracy.

The detergents may contain the polyesters according to the invention in the form of any of their water-soluble salts and preferably in the form of their alkali metal and ammonium salts. The term ammonium salts is intended also to include the salts of the polyesters with organic ammonium bases. The polyesters can be added to the detergents in the form of their free acids, providing alkalinely reacting substances are present in a sufficiently great excess for the formation of salts.

In addition to the salts of the polyesters, the new detergents and cleansing agents contain the surface-active substances customarily used in such agents, such as those of the sulfate or sulfonate type, for example, the primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated fatty alcohols, and alkylbenzenesulfonates, primary and secondary olefin sulfonates, alkyl sulfonates and u-sulfofatty esters. Additional compounds of this class which may be 'used are the high molecular weight sulfatized partial ethers and partial esters of polyvalent alcohols; the sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols; fatty acid taurides and fatty acid isoethionates and homologues thereof. Also suitable are the alkali soaps of fatty acids as well as the fatty acid condensation products of amino acids or degraded proteins; and ampholytes such as alkylbetaines and alkylsulfobetaines. The agents can furthermore contain non-ionic wash-active substances, such as alkyl and acyl polyglycolethers, co'condensation products of polyethylene glycol and polypropylene glycol, fatty acid sugar esters, aminoxides and fatty acid alkanolamides. Any of the foregoing compounds can also be used in the form of mixtures thereof. If the compounds have an aliphatic hydrocarbon radical, the latter is preferably to be straight-chained and have 8 to 22 carbon atoms. In compounds having araliphatic hydrocarbon radicals, the preferably unbranched alkyl chains contain an average of 6 to 16 carbon atoms.

Furthermore, depending on the purpose for which they are intended, the new detergents and cleansers can contain other conventional components such as pyrophosphates, polyphosphates and the more highly condensed phosphates, as well as silicates, in the form of their alkali salts; oxygen-yielding bleaches or bleaches containing active chlorine, such as alkali perborates, alkali percarbonates, alkali hypochlorites, chlorinated cyanuric acids and their alkali salts; as well as neutral salts such as magnesium silicate and sodium sulfate. Furthermore, sequestering agents may be present, particularly alkali salts of aminopolycarboxylic acids, e.g., the sodium salts of aminotriacetic acid or of ethylenediaminotetraacetic acid and the alkali salts of hydroxyalkyldiphosphonic acids and aminopolyphosphonic acids, such as the disodium salt of l-hydroxyethane-l,l-diphosphonic acid or the hexasodium salt of aminotri-(methylenephosphonic acid).

Substances for the regulation of the pH can also be components of the mixture. These include sodium carbonate, sodium bicarbonate, lactic acid and citric acid and the like.

The detergents can also contain optical brighteners, such as the derivatives of diaminostilbenedisulfonic acid or of diarylpyrazolinesulfonic acid. To control sudsing action the detergents may contain suds improvers, such as fatty acid amides, or anti-foaming agents, particularly trialkylmelamines.

The new detergents and cleansers may be in solid form, and preferably powder form, or in the form of solutions or pastes. Because of the excellent water solubility of the polyester salts they are particularly well suited for the manufacture of liquid detergent concentrates. Such liquid preparations may contain, in addition, to the above-named components, hydrotropic substances such as alkylbenzenesulfonates of low molecular weight, urea, and organic solvents.

In a number of cases, especially in the washing of textile materials made of cellulose or regenerated cellulose, the cleansing action can be further improved by the addition of standard graying inhibitors, particularly carboxymethylcellulose. The amounts of carboxymethylcellulose to be used will be approximately from 0.1 to 3% of the total weight of the detergents.

The new detergents of the invention are suitable for the cleaning of articles of all kinds, but particularly for the washing of textiles which are made of synthetic fibers, cellulose fibers, regenerated cellulose, or of mixtures of the aforesaid types of fibers. In comparison with detergents of the prior art, the new detergents make the washing process itself easier and improve the whiteness of the laundry.

The following examples are given for the purpose of illustrating the invention and are in nowise to be construed as a limitation thereof.

The gray-inhibiting action of the compounds described in the following examples was tested by known methods and include the following:

6 (A) The redeposition method (also known as the Example 1 rewash method) involving the washing together of dirty and clean textile material. 385 g. (2 moles) of anhydrous cltrlc acld, 125 g. (2 (B) the deposition method, in which clean textiles molcs) of anhydrous thylene glycol and 500 ml. of Y- are washed in an artificially dirtied wash w t lene were heated together with one drop of concentrated ET 5 sulfuric acid in a distillation apparatus which was (A) REDEP-OSmON HOD equipped with a system for separating the water and feed- In each test 4 cloth samples, each made of Baumwollin; back m: solvent The heating was continued mm renforc or of synthetic fabric weighing a i of no further water of reaction was separated in the received. :3 g rsx g g ggg g i gflg g gg fg The xylene was decanted from the insoluble resin that had 5 i' (Atlas g U S A g formed, and the rcsldue was drled ln vacuo. The polyester after, the reflectivity ot' the thusly washed samples was g g 3L33 :23? gg i gg 3 light (Elrepho Cad Zelss equlpwd tralized with dilute sulfuric acid and the neutral solution with a No. 6 filter).

ad usted to provlde a polyester content of 10 g./l. Ap- The reallstlcally slmulated dust sebum comblnatlon pmpriaw cums of this solution were added to the used for soiling the cotton yarn consisted of a mixture of kaolin, iron oxide black, carbon black and synthetic g i h m e I dun the followin w m sebum (prepared from a mixture of Va fatty acids, to fat acted g e m p g c and /3 hydrocarbons). The cotton yarn contained ap- Acid Alcohol Example:

2 1 mole of citric acid 1 mole of LG-hemnediol.

3... do 1 mole dodecyldiethanolarnine.

4 1 mole nitlilotriacetic acid 1 mole 1,6-hexanedlol.

5.- 1 mole pyromellitic acid Do.

6 Mixture of, 0.6 mole nltrilotriacetic acid, and 0.5 mole malelc acid 1 mole ethylene glycol.

proximately 11% pigments and about 2% sebum after The results of the washing tests are shown in the folsoiling. lowing table. The vdegree of graying of polyester fabrics, The detergent which was used in the washing of these cotton fabrics and cotton-polypropylene mixture fabrics samples had the following composition: was determined by Method A (redeposition method) after mdodecYlbenzenesulionate (sodium Salt) five washlngs in each case. The experiments with Perlon 2.5% coconut fatty alcohol Sulfate (sodium salt) fabrlcs and with a mlxture fabric made of 67% polyester 2.5% tallow fatty alcohol sulfate (sodium salt) 33% Wm l? by B l 40% sodium pyropbosphate tlon method). The abbreviation CMC as used hereinafter 0% graying inhibitor 40 designates carboxymethylcellulose, which was used in 35 25% sodium sulfa each case as comparison substance. 7

The concentration of detergent in the wash water f l 52 the g i i acco ln emven naseom r car xme amounted to 5 grams per liter and the hardness of the ll l pa y y tap water to 10 dH. The cotton samples were washed at 90 C. for 30 minutes at a goods-to-wash-water ratio TABLE I of 1:12 (wash water lfS ml,), and the synthetic fabric i ill lgi samples were washed at C. for 30 minutes at a goodslfihibitolr a nt l atlor i l glz to-wash-water ratio of 1:30 (wash water 290 ml.). The samples were then rinsed four times with distilled water, substrate (Method A) 0 dried and ironed, and evaluated photometrically, 50 Polyester (13101011 i 3.8 (B) DEPOSITION METHOD 3 it 1%.? 211 131 The tests in the deposition method were carried out 421i 1 1 18 using skein goods in the Terg-Ometer (United States 6 44.1 46.0 46.8 4.8.0 Testinlg3 Company, Hoboken, U.S.A.). Ten-gram skeins of cfitompoly-propylenemlxturefabone 35 4 a 43 46 0 th su Stance to be evaluated were washed in one liter of c .6 .8 wash water (gOods-to-wash-water ratio 1:100) with the Hummus 3 addition of 0.2, 0.5, and 1.0 and 1.5 g. of standardized g 3%: $3 3-; carbon black (Degussa 100) plus 5% of the grayin i hibitor being tested in each case. 0

The detergent which was used in these tests consisted of Percent reflectance at l7l:lld/lprC1il::,adl.lOn1b:3Vlng K3111: follonliicomptiztlon. m g g. n ecy nzenes ona e lum sa l e 1.1 g./l. coconut fatty alcohol sulfate (sodium salt) substme (Memw B) M L5 1.1 g./l. tallow fatty alcohol sulfate (sodium salt) gggg g 3 g a g: 16.0 g./l. sodium pyrophosphate 3 71 67 61 m 14.0 g./l. sodium sulfate 5 71 56 57 56 5-0 g-/ graying inhibitor Polyester-cotton mixture 49 38 a0 27 Fabric a 57 4s 46 In each case, 100 ml. of this stock solution was diluted 70 to one liter with tap water of 10 dB. The samples were washed at 60 C. for 10 minutes with the TergPOmeter We claim: operating at 100 r.p.m. The samples were then rinsed with A ge t composition consisting essetially of a distilled water three times, dried and photometrically detergent selected from the group consisting of anionic, evaluated. 75 ampholytic, and non-ionic synthetic detergents and mixtures thereof, and a graying inhibitor in an amount from 0.1 to 20 weight percent based on the total weight of said composition, said graying inhibitor being selected from the group consisting of the alkali metal and ammonium salts of aresin-like, water and xylene insoluble, polyester containing free-carboxyl groups, the acid radical of said polyester being derived from a polyvalent carboxylic acid selected from the group consisting of citric, tricarballylic, nitrilotriacetic, ethylene diaminotetracetic, cyclohexanetriacetic, trimesic, oxytrimesic and pyromellitic acids, and the'alcohol radical of said polyester being derived from a bivalent alcohol from the group consisting of bivalent aliphatic alcohols and amino alcohols, said aliphatic alcohols containing 2 to 18 carbon atoms in the molecule and said amino alcohols being substituted at the nitrogen atom thereof by an alkyl radical having 1 to 18 carbon atoms and containing two alkylol radicals having 1 to 3 carbon atoms, the mole ratio of said polyvalent carboxylic acid to said bivalent alcohol derived radicals in said polyester being in the range of l.l:0.9 to 0.9:], said graying inhibitor being prepared by:

(a) preparing a water and xylene insoluble polyester resin by reacting 1) said polyvalent carboxylic acid or an anhydride thereof, with (2) said bivalent al- 8 cohol in the presence of an esterification catalyst and with removal of the water of reaction, and

(b) dissolving the resin thus obtained in a basic solution containing a cation of said alkali metal or ammonia.

2. The composition of claim 1 wherein said bivalent alcohol is selected from the group consisting of ethylene glycol, hexanediol and N-dodecyldiethanolamine.

3. The composition of claim 1 wherein up to 50 mol percent of said polyvalent carboxylic acid reacting with said bivalent alcohol is replaced with a dicarboxylic acid selected from the group consisting of malonic, succinic, glutaric, adipic, sebacic, maleic and fumaric acids.

References Cited UNITED STATES PATENTS 3,284,364 11/1966 Siegele 252-461 LEON D. ROSDOL Primary Examiner ARNOLD RADY, Assistant Examiner US. Cl. X.R. 

